Method of combating weeds



United States Patent 6 3,298,817 METHOD OF COMBATING WEEDS Harry Tilles, 703 Balra Drive, El Cerrito, Calif. 94530, and Joe Antognini, 22362 Freemont Drive, Mountain View, Calif. 94040 No Drawing. Filed Apr. 16, 1959, Ser. No. 806,779 9 Claims. (Cl. 712.6)

This application is a continuation-in-part of our application Serial No. 753,891, filed August 8, 1958, now abandoned.

This invention relates to certain chloroalkyl and bromoalkyl esters of disubstituted thiolcarbamic acids as herbicides, and as new compounds. More specifically, the invention relates to compounds of the general formula :1 R1S-ON wherein R is a lower chloroalkyl or bromoalkyl radical, R is a lower alkyl radical, a lower chloroalkyl radical, a lower alkenyl radical, a lower chloroalkenyl radical or an alkynyl radical, and R is a lower alkyl radical, a lower cycloalkyl radical, a lower chloroalkyl radical or a lower alkenyl radical. Typical non-limiting examples of the various substituents are as follows:

R1 R2 R3 ClCHgCHz CQHE CzHs (It-2217) ClCHzCHz 11-0 117 IlC:;H1 (13-2215) ClCHgCHz CH3 I1-O4Ho (Rx-2513) ClCHzCHg CzHs I1-C4Hn (It-2514) ClCH2CH2 C2115 eyelohexyl (11-2515) ClCHzCIL CH2=CHCHz CHZ=CHCH2 11-2516) ClCHzCHz CHz= CHCHz Il-C3H7 (R-2503) CICHgCHz CI'I2=CHCHz i-C3H7 (IX-2517) CICI'IZCHZ CH2= CHCHz l-CAHU (18-2505) ClCHzCHz CH2=C(C1)CH2 n-C3H7 (IR-2507) ClCHzCHz CHz=C(C1)CH2 CH2=CHCH2 (R-2508) C1CH2CH2 ClCH= CHCHZ C2115 (lit-2509) ClCHzCHz CICH CHCHz n-CaH-r (R-2525) ClCHzCHz CH2=C(CH3) CH2 CzHs (Ii-2518) ClCHzCHg CI-Iz= C (CH3) CH2 Il-C3Hl (It-2519) CICHzCHz CH2=C(CH:;) CH3 CH2=CHOH2 (IR-2520) ClCHzCHz HC CCH: n-C3H1 (It-2523) ClCHzCH2 C1CH2CH9 ClCHzCHz (R-2526) ClCHzCI-Iz CHaCHClCHz CH3CHC1CH2 (R-2527) CICHzCHzCHz C2115 C2135 (RZ626) ClCHzCHzCHz D-CaH- n-CaH7 (It-2629) C1CH2CH2CH2 C2115 11-C1H9 (11-2632) ClCHzCHzCHa CH2= CHCHz CH2= CHCH: (It-2630) ClCHzCHzCHz CHz=CHCH2 11-03117 (11-2633) ClCHzCHzCI-Iz CHz=C-(CH3) CH2 Il-C3H7 (B-2634) C1CH2CH2C1'I2 CHz=C(CH3)CHz CH2=CHCH2 (It-2636) CICHzCHzCHz CHz=C(Cl)CH2 Il-Ca (R-2G40) ClCHzCHzCHz C1CH=CHCH2 CH2=CHCH2 (R-2641) ClCH2CH2CH2 HC CCHZ n-C H1 (Ii-2643) CICHQCI'IZCH2 ClCHzCHz ClCHzCHi R-2644) BrCHgCHz @2115 1-15 (It-2939) BrCHzCHz 11-C5H7 n-CaH7 (IR-2941) BICHzCHz n-CrHa CzH (It-Z946) BrCHzCHg CHz=CHCH5 OHz=CHCH5 (R-2948) :BI'CH2CH2 CH2=OHCH2 Il-C3H7 (Ii-2949) BICHQCHQ CHz=C(CH3)CH2 CzH (R2952) BICHzOHz CHz=C(CHa) CH2 CH=CHCH2 (R-2958) BrCHzCHzCHg C H5 2 5 (Br-2962) BrCH2CHzCI-I2 n-C3H7 11-C3H7 (It-2969) BICHzCHzCHz 11 C411 CH3 (R-2978) BrCHzCHzCHz CHz=CHCHz CHz=CHCHg (IR-2984) BrcHzcHzCHz CHz= CH CH2 lit-03H! (R-2987) BICHzCHzCHz CH2=C(CH3) CH3 C 11 (It-2990) The novel compounds of the present invention may be made in accordance with the following non-limiting examples. Code numbers have been assigned to each compound and are used throughout the balance of the application.

Example I (R-2217).8.5 g. (0.048 mole) of 2-hydroxyethyl N,N-diethylthiolcarbamate was dissolved in 25 cc. of benzene and 1 drop of pyridine was added. The solution was cooled to 2 /2 C. and 7.2 g. (0.060 mole) of thionyl chloride was rapidly added. The temperature of the mixture rose rapidly to 24 C. while still in the ice 3,298,817 Patented Jan. 17, 1967 bath and slowly to 35 C. after removal from the ice'bat'h. The mixture was then brought to reflux, held at reflux for /2 hour, cooled to room temperature, diluted with cc. of ethyl ether and washed with three-25 cc. portions of water. The ether solution was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated on the steam bath. The residual liquid was fractionally distilled. There was obtained 6.8 g. (72.2% yield) of 2-chloroethyl N,N-diethylthiolcarbamate, B.P. (20 mm.) 144-145 C., n 1.5011.

Analysis.Calculated for C H ClNOS: N=7.16%; Cl=18.1%. Found: N=7.05%; Cl=18.06%.

Example II (R-2503).1.00 g. (6.29 10- moles) of 2-chloroethyl chlorothiolformate was dissolved in 10 cc. of ethyl ether and a solution of 1.40 g. (13.8 X 10- moles) of N-allyl-n-propylamine in 15 cc. of ethyl ether was added rapidly. An exothermic reaction ensued and N- allyl-n-propylamine hydrochloride precipitated. 10 cc. of water was added, the mixture was transferred to a separatory funnel, 25 cc. more ethyl ether was added and the aqueous layer was separated. The ether layer was then washed with two-10 cc. portions of dilute hydrochloric acid (1 cc. of concentrate hydrochloric acid made up to a volume of 10 cc. with water) and one-10 cc. portion of water. The ether solution was then dried over anhydrous magnesium sulfate, filtered and evaporated on a warm hot plate under a stream of argon. There was obtained as a residual liquid 1.24 g. (89% yield) of 2-chloroethyl N- allyl-N-n-propylthiolcarbamate, 11 1.5068.

Analysis.-Calculated for C H ClNOS: N=6.32%. Found: N=6.30%.

Example 111 (R2505)When the general procedure of Example II was repeated except that 1.00 g. (6.29 10- moles) of 2-chloroethyl chlorothiolformate and 1.56 g. (13.8)(10 moles of N-allyl-i-butyl amine were employed, there was obtained 1.48 g. (63.5% yield) of Z-chloroethyl N--allyl-N-i-butylthiolcarbamate, #1 1.5018.

Analysis.-Calculated for C H ClNOS: Found: N=6.04%.

Example I V (R2507).When the general procedure of Example II was repeated except that 1.00 g. (6.29 10- moles) of 2-chloroethyl chlorothiolformate and 1.84 g. (13.8 10 moles) of N-Z-chloroallyl-n-propylamine were employed, there was obtained 1.40 g. (87% yield) of 2-chloroethyl N-Z-chloro-N-n-propylthiolcarbamate, n 1.5181.

Analysis.Calculated for C H Cl NOS: N=5.47%. Found: N=5.71%.

Example V (R2508).When the general procedure of Example II was repeated except that 1.00 g. (6.29 10 moles) of Z-chloroethyl chlorothiolformate and 1.82 g. (13.8 10- moles) of N-Z-chloroallyl-allylamine were employed, there was obtained 1.46 g. (91.3% yield) of 2-chloroethyl N-2-chloroallyl-N-allylthiolcarbamate, n 1.5291.

Analysis.Calculated for C H Cl NOS: N=5.51%. Found: N=5.51%.

Example VI (R2509).When the general procedure of Example II was repeated except that 1.00 g. (6.29 10 moles) of 2-chloroethyl chlorothiolformate and 1.65 g. (13.8 l0 moles) of N-3-chloroallyl-ethylamine were employed, there was obtained 1.39 g. (91.5% yield) of 2-chloroethyl N-3-chloroallyl-N-ethylthiocarbamate, 11 1.5283.

Analysis.Calculated for C H Cl NOS; N=5.78%. Found: N=5.93%.

Example VII (R2215).When the general procedure 7 of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 1.82 g. (18.0 10- moles) of di-n-propylamine were Example IX (R-25I4).When the general procedure of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 1.82 g. (18.0 10 moles) of N-ethyl-n-butylamine were employed, there was obtained 1.77 g. (96.8% yield) of 2-chloroethyl N-ethyl-N-n-butylthiolcarbamate, 11 1.4940.

Analysis.Calculated for C H ClNOS: N=6.27%. Found: N=6.55%.

Example X (R25I5).When the general procedure of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 2.28 g. (18.0 10 moles) of N-ethylcyclohexylamine were employed, there was obtained 2.02 g. (99.0% yield) of 2-chloroethyl N-ethyl-N-cyclohexylthiolcarbamate, 11 1.5143.

Aaalysis.Calculated for C H ClNOS: N=5.61%. Found: N=5.50%.

Example XI (R25I6).When the general procedure of Example II was repeated except that 1.30 g. (8.l8 10' moles) of 2-chloroethyl chlorothiolformate and 1.75 g. (18.0 10 moles) of diallylamine were employed, there was obtained 1.65 g. (91.6% yield) of 2-chloroethyl N,N-diallylthiolcarbam-ate, n 1.5180.

Analysis.Calculated for C H CINOS: N=6.38%. Found: N=6.23%.

Example XII (R25I7).When the general procedure of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 1.78 g. (18 10 moles) of N-allyl-i-propylamine were employed, there was obtained 1.73 g. (95.5% yield) of 2-chloroethyl N-allyl-N-i-propylthiolcarbamate, n 1.5090.

Analysia-Calculated for C H CINOS: N=6.32%. Found: N=6.36%.

Example XIII (R-25I8).When the general procedure of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 1.78 g. (18x10 moles) of N-rnethallylethylamine were employed, there was obtained 1.28 g. (70.6% yield) of 2-chloroethyl N-methallyl-N-ethylthiolcarbamate, n 1.5080.

Analysis.Calculated for C H ClNOS: N=6.32%. Found: N=6.48%.

Example XIV (R25I9).When the general procedure of Example II was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 2.04 g. (18.0 10 moles) of N-methallyl-n-propylamine were employed, there was obtained 1.77 g. (91.7% yield) of 2-chloroethyl N-methallyl-N-n-propylthiolcarbamate, n1 1.5029.

Analysis.Calculated for C H ClNOS: N=5.94%. Found: N=5.82%.

Example XV (R2520).When the general proce- Example XVI (R2523).-When the general procedure of Example 11 was repeated except that 1.30 g. (8.18 10 moles) of 2-chloroethyl chlorothiolformate and 1.75 g. (l8.0 10 moles) of N-propargyl-n-propylamine were employed, there was obtained 1.74 g. (96.7% yield) of 2-chloroethyl N-propargyl-N-n-propylthiolcarbamate, r1 1.5123. g r U Analysis.-Calculated for C H CINOS: N=6.38%. Found: N=6.19%. 7

Example XVII (R2525).When the general proce= dure of Example II was repeated except that 1.30 g.- (8.18 10- moles) of 2-chloroethlyl chlorothiolformate and 2.40 g. (18 10 moles) of 3-chloroal-lyln-propylamine were employed, there was obtained 2.03 g. (96.6% yield) 2-chloroethyl N-3-chloroallyl-n-propylthiolcarba= mate, n 1.5196.

Analysis.Calculated for C I-I Cl NOS: N:5.47%. Found: N=5.38%.

Example XVIII (R-2526).1.30 g. (818x10- moles) of 2-chloroethyl chlorothiolformate was dissolved in 25 cc. of ethyl ether and 1.75 g. (9.81 10 moles) of bis (2-chloroethylamine hydrochloride) was added. The mixture was cooled to 3 C. in an ice bath and then 10 cc. of aqueous sodium hydroxide solution containing 0.67 g. (16.8 10 moles) of sodium hydroxide was slowly added. After the addition was complete, the reaction mixture was allowed to warm up to room temperature and was then worked up in the same manner 218 Example II. There was obtained 1.96 g. (90.3% yield) of 2-chloroethyl N,N-bis(2-chloroethyl)thiolcarbamate, 11 1.5381.

Analysis.Calculated for C H C-l NOS: N=5.29%. Found: N=5.49%.

Example XIX (R2527).When the eneral proce dure of Example XVIII was repeated except that 1.30 g. (8.l8 10 moles) of 2-chloroethyl chlorothiolformate, 2.03 g. (9.81 x 10" moles) of his (2-chloropropylamine) hydrochloride and 0.67 g. (16.8 10" moles) of sodium hydroxide were employed, there was obtained 2.19 g. (91.3% yield) of 2-chloroethyl N,N-bis (2-chloropropyl) thiolcarbamate, n 1.5196.

Analysis.-Calculated for C H Cl NOS: N=4.78%. Found: N=4.92%.

Example XX (R-2626).-3.8 g. (0.052 mole) of (llethylamine dissolved in 50 cc. of ethyl ether was added to 2.0 g. (0.05 mole) of sodium hydroxide dissolved irl 50 cc. of water. The mixture was cooled to 5 C. and then 8.7 g. (0.05 mole) of 3-chlor0propyl chlorothiolformate was added dropwise with stirring maintaining the temperature between 5l0 C. The mixture was then allowed to warm up to room temperature and was then worked up in the same manner as Example II. There was obtained 7.5 g. (71.3% yield) of 3-chloropropyl' N,N-di-ethylthiolcarbamate, RP. (10 mm.) 1420-1428 C., 11 1.4989.

Analysls.-Calculated for C H ClNOS: Cl=16.90%; N=6.68%. Found: Cl=17.01%; N=6.66%.

Example XXI (R-2629).When the general proce dure of Example XX was repeated except that 5.3 g. (0.052 mole) of di-n-propylamine, 8.7 g. (0.05 mole) of 3-chloropropyl chlorothiolformate and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 6.4 g. (54.0% yield) of 3-chloropropyl N,N-di-n-propylthiolcarbamate, B.P. (10 mm.) 158.5159.0 C., n 1.4925.

Analysis-Calculated for C H CINOS: Cl=14.91%; N=5.89%. Found: Cl=15.12%; N=5.78%.

Example XXII (R-2632).-When the general procedure of Example XX was repeated except that 5.3 g. (0.052 mole) of N-ethyl-n-butylamine, 8.7 g. (0.05 mole) of 3-chloropropyl chlorothiolformate and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 7.5 g. (63% yield) of 3-chloropropyl N-ethyl-N-nbutylthiolcarbamate, B.P. (10 mm.) 161.5162.0 C., n 1.4929

.Analysis.Calculated for C I-I ClNOS: C1=14.91%; N=5.89%. Found: Cl:14.91%; N=5.81%.

Example XXIII (R2630).-When the general procedure of Example XX was repeated except that 5.1 g. (0.052 mole) of diallylamine, 8.7 g. (0.05 mole) of 3- chloropropyl chlorothiolformate and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 8.9 g. (76.5% yield) of 3-chl0ropropyl N,N-diallylthiolcarbamate, B.P. mm.) 159.0-l59.5 C., n 1.5147.

Analysis.Calculated for C H ClNOS: Cl=15.17%; N=5.99%. Found: C1=15.08%;N=5.85%.

Example XXIV (R2634).When the general procedure of Example XX was repeated except that 11.8 g. (0.103 moles) of N-methallyl-n-propylamine, 17.3 g.

(0.10 mole) of 3-chloropropyl chlorothiolformate and 4.0

g. (0.10 mole) of sodium hydroxide were employed, there was obtained 19.7 g. (78.8% yield) of 3-chloropropyl N-methallyl-N-n-propylthiolcarbamate, B.P. (10 mm.) 164.0-164.1 C., n 1.5013.

Analysis.-Calculated for C I-I CINOS: Cl: 14.19%; N=5.61%. Found:Cl=13.94%;N=5.53%.

Example XXV (R2636).When the general procedure of Example XX was repeated except 5.8 g. (0.052 mole) of N-methallylallylamine, 8.7 g. (0.05 mole) of 3-chloropropyl chlorothiolformate and 2.0 g. of sodium hydroxide were employed, there was obtained 8.9 g. (71.6% yield) of 3-chloropropyl N-Inethallyl-N-allylthiolcarbamate, B.P. (10 mm.) 163.5-164.0C., 11 1.5113.

Analysis.-Calculated for C I-I ClNOS: Cl=14.31%; N=5.65%. Found: Cl=14.51%; N=5.69%.

Example XX VI (R2640).When the general procedure of Example XX was repeated except 4.0 g. (0.03 mole) of N-2-chloroallyl-n-propylamine, 5.0 g. (0.029 mole) of 3-chloropropyl chlorothiolformate 'and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 6.9 g. (87.5% yield) of 3-chloropropyl N-2- chloroallyl-N-n-propylthiolcarbamate, 11 1.5148.

Analysis.-Calculated for C H Cl NOS: Cl=26.24%. Found: Cl=26.47%. Molar refraction: Calcd.: 69.52. Found: 69.56.

Example XX VII (R-264I).-When the general procedure of Example XX was repeated except that 3.9 g. (0.03 mole) of N-3-chloroallylallylamine, 5.0 g. (0.029 mole) of 3-chloropropyl chlorothiolformate and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 6.8 g. (87.2% yield) of 3-chloropropyl N-3- chloroallyl-N-allylthiolcarbamate, 21 1.5312.

Analysis.Calculated for C H Cl NOS: C1=26.44%. Found: Cl=26.64%. Molar refraction: Calcd: 69.20. Found: 68.70.

Example XX VIII (R2643).-When the general procedure of Example XX was repeated except that 5.1 g. (0.052 mole) of N-propargyl-n-propylarnine, 8.7 g. (0.05 mole) of 3-chloropropyl chlorothiolformate, and 2.0 g. (0.05 mole) of sodium hydroxide were employed, there was obtained 6.2 g. (53.1% yield) of 3-chloropropy1 N-propargyl-N-n-propylthiolcarbamate, B.P. (10 mm.) 167.0167.5 C., 11 1.5117.

Analysis.-Calculated for C H ClN-OS: Cl=15.17%; N=5.99%. Found: Cl=15.31%; N=5.83%.

Example XXIX (R2644).When the general procedure of Example XVIII was repeated except that 5.4 g. (0.03 mole) of bis(2-chloroethylamine) hydrochloride, 5.0 g. (0.029 mole) of 3-chloropropyl chlorothiolformate and 2.4 g. (0.06 mole) of sodium hydroxide were employed, there was obtained 7.7 g. (95% yield) of 3-chloropropyl N,N-bis(2-chloroethyl) thiolcarbamate, 11 1.5330.

Analysis.Calculated for C H Cl NOS: Cl=38.17%. Found: Cl=38.39%.

Example XXX (R2633).When the general procedure of Example XX was repeated except that 5.2 g. (0.052 mole) of N-allyl-n-propylamine, 8.7 g. (0.05 mole) of 3-chloropropyl chlorothiolformate and 2.0 g.

6 (0.05 mole) of sodium hydroxide were employed, there was obtained 8.47 g. (71.8% yield) of 3-chloropropyl N allyl N n propylthiolcarbamate, B.P. (10. mm.) 159.5-160.0 C., 12 1.5037.

Analysis.Calculated for C H ClNOS: Cl=15.04%; N=5.94%. Found: Cl=15.13%; N=5.96%.

Example XXXI (R-2939).-A 500 cc. 4 neck flask was provided with stirrer, thermometer, condenser and gas inlet tube. A solution of 7.3 g. (0.10 mole) of diethylamine and 10.1 g. (0.10 mole) of triethyla-mine in 150 cc. of tert. butyl alcohol was changed to the flask and then 10 -g. (0.17 mole) of carbonyl sulfide was bubbled into the amine solution with rapid stirring maintaining the temperature between 15-20 C. with ice cooling. To this solution at 15 C. was then added rapidly 56.4 g. (0.30 mole) of 1,2-di bromoethane. The mixture was then heated slowly to 45 C. and was maintained at 4550 C. for 1 /2 hours. The thin slurry was then heated to reflux, cc. of solvent was distilled, the residual slurry was cooled to room temperature, diluted with 200 cc. of petroleum ether, B.P. 3060 C., and successively washed with 250 cc. portions of 5% hydrochloric acid and 2-50 cc. portions of water. The organic phase was then dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated on the steam bath. The residual liquid was then fractionally distilled through an 18 Pod-bielniak Hel-i-G-rid Fractional Distillation Column. There was obtained 12.6 g. (52.5% yield) of 2- bromoethyl N,N-diethylthiolcarbamate, B.P. (10 mm.) 139l40 C., n 1.5229.

Analysis.-Calculated tor CqHmBI'NOSI N, 5.83%. Found: N, 5.97%.

Example XXXII (R-294I ).--When the general procedure of Example XXXI was repeated except that 10.1 g. (0.10 mole) of di-n-propylamin-e, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 56.4 g. (0.30 mole) of 1,2-di bromoethane and cc. of tert. butyl alcohol were employed, there was obtained 13.5 g. (50.2% yield) of 2 bromoethyl N,N-di-n-propylthiolcarbamate, B.P. (10 mm.) 155.5156.0 C., 11 1.5122.

Analysis.-Calculated tor C H BrNOS: N, 5.22%. Found: N, 4.95%.

Example XXXIII (IQ-2946) .When the general procedure of Example XXXI was repeated except that 10.1 g. (0.10 mole) of N-ethyl-n-butylamine, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 56.4 .g. (0.30 mole) of. l,2-dibrornoethane and 150 cc. of tert. butyl alcohol were employed, there was obtained 9.6 'g. (35.8% yield) of 2a-bromoethyl N-ethyl-N-n-butylthiocarbamate, B.P. (10 mm.) 157.0159.5 C., n 1.5118.

Analysis.--Calculated for C H BINOS: N, 5.22%. Found: N, 5.44%.

Example XXXI V (R-2948) .When the general procedure of Example XXXI was repeated except that 9.7 g. (0.10 mole) of diallylaimine, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 5 6.4 g. (0.30 mole) of 1,2-dibromoethane and 150 cc. of tert. butyl alcohol were employed, there was obtained 9.8 g. (37.0% yield) of Z-bromoethyl N,Ndiallylthiolcarlbamate, B.P. (10 mm.) l54.0156.5 C., n 1.5368.

Analysis.-Calculated for C H BINOS: N, 5.30%. Found: N, 5.51%.

Example XXX V (R2949).-When the general procedure of Example XXXI was repeated except that 9.9 g. (0.10 mole) of N-allyl-n-propylarnine, 10ml g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 56.4 g. (0.30 mole) of 1,2-dibromoethane and 150 cc. of tert. butyl alcohol were employed, there was obtained 14.7 g. (55.3% yield) of Z-bromcethyl N-allyl-N-n-propylthiocarbamate, B.P. (10 mm.) l55.0156.5 C., n 1.5270.

Analysis.Calcula-ted for C H BrNOS: N, 5.26%.. Found: N, 5.22%.

Example XXXVI (R-2952).-When the general procedure of Example XXXI was repeated except that 9.9 g. (0.10 mole) of Namethallylethylamine, 10.1 g. (0.10 mole) of trietliylamirie, 10 g. (0.17 mole) of carbonyl sulfide, 56.4 g. (0.30 mole) of 1,2-dibr-moethane and 150 cc. of. tert. butyl alcohol were employed, there was obtained 12.8 g. (48.0% yield) of 2-brom0ethyl N- methallyl-N-ethylthiolcarbamate, B.P. mm.) 151.0- 153.0 C., n 1.5267.

Analysis.Calculated for C H B rNOS: N, 5.26%. Found: N, 5.45%.

Example XXX VII (R2958).When the general procedure of Example XXXI was repeated except that 11.1 g. (0.10 mole) of N-methallylallylamine, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 56.4 g. (0.30 mole) of 1,2-d-ibromoethane and 150 cc. of tert. butyl alcohol were employed, there was obtained 12.6 g. (45.3% yield) of Z-brornoethyl N-methallyl-N-allylthiolcarbamate, B.P. (10 mm.) 160.016l.0 C., n 1.5320.

Analysis.Calculated for C H BrNOS: N, 5.03%. Found: N, 5.25%.

Example XXX VIII (R2962).When the general procedure of Example XXXI was repeated except that 7.3 g. (0.10 mole) of diethylamine, 10.1 g. (0.10 mole) of triethylarnine, 10 g. (0.17 mole) of carbonyl sulfide, 60. 6 g. (0.30 mole) of 1,3-di'bromopropane and 150 cc. of tert. butyl alcohol were employed, there was obtained 15.3 g. (60.2% yield) of. 3-brom-opropyl N,N-diethylthiolca-rbarnate, B.P. (10 mm.) 152.5153.5 C., n 1.5166.

Anaheim-Calculated for C H BrNOS: N, 5.51%. Found: N, 5.57%.

Example XXXIX (R-2969) .When the general procedure of Example XXXI was repeated except that 10.1 g. (0.10 mole) of di-n-propylamine, 10.1 'g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 60.6 g. (0.30 mole) of 1,3-di br0mopropane and 150 cc. of tert. butyl alcohol were employed, there was obtained 18.4 g. (65.4% yield) of 3-bromopr=opyl N,N-di-n-propylthiolca-rbamate, B.P. (10 mm.) 169.5171.0 C., n 1.5078.

Analysis.-Calculated for C H BrNOS: N, 4.96%. Found: N, 5.05%.

Example XL (R2978).When the general procedure of Example XXXI was repeated except that 8.7 g. (0.10 mole) of N-methyl-n-butylamine, 10.1 g. (0.10 mole) of triethylarnine, 10 g. (0.17 mole) of carbonyl sulfide, 60.6 :g. (0.30 mole) of 1,3-dibromopropane and 150 cc. of tert. butyl alcohol were employed, there was obtained 14.7 g. (54.8% yield) of 3-br0mopropyl N-nbutyl-N-methylthiolcanba mate, B.P. (10 mm.) 164.5- 167.0" C., n 1.5111.

Analysis.Calc-ulated for C H BrNOS: N, 5.22%. Found: N, 5.13%.

Example XLI (R2984).When the general procedure of Example XXXI was repeated except that 9.7 g. (0.10 mole) of diallylamine, 10.1 g. (0.10 mole) of triethyla-mine, 10 g. (0.17 mole) of carbonyl sulfide, 60.6 g. (0.17 mole) of 1,3-dibromopropane and 150cc. of tert. butyl alcohol were employed, there was obtained 12.2 g. (43.4% yield) of 3-bromopropyl N,N-diallylthiolcarbamate, B.P. (10 mm.) 165.0-167.0 C., 11 1.5283.

Analysis.Calculated for C H BrNOS: N, 5.03%. Found: N, 5.00%.

Example XLII (R2987).When the general procedure of Example XXXI was repeated except that 9.9 g. (0.10 mole) of N-allyl-n-propylarnine, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 60.6 g. (0.30 mole) of 1,3-dibromopropane and 150 cc. of tert. butyl alcohol were employed, there was obtained 17.8 g. (63.6% yield) of 3-bromopropyl N-allyl- N-n-propllthiocarbama-te, B. P. (10 mm.) 169.0-170.0 C., n 1.5190.

Analysis.Calculated for C H BrNOS: N, 5.00%. Found: N, 4.95%.

Example XLIII (R2990).When the general procedure of Example XXXI was repeated except that 9.9 g. (0.10 mole) of N-niethallylethylamine, 10.1 g. (0.10 mole) of triethylamine, 10 g. (0.17 mole) of carbonyl sulfide, 60.6 g. (0.30 mole) of 1,3-dibromopropane and 150 cc. of tert. butyl alcohol were employed, there was obtained 15.4 g, (55.0% yield) of 3-bromopropyl N-metha1lyl-N-ethylthiolcarbamate, B.P. (10 min.) 164.0 165.5 C., n 1.5200.

Analysis.Calculated for C H BrNOS: N, 5.00%. Found: N, 4.99%.

The compounds of the present invention have been tested as herbicides and found very effective as the following typical tests show. Some of the compounds are quite selective in their action and can be used to eradicate or control one type of plant, while another type of plant is relatively unaffected.

In making the following tests, seeds were planted in 3" pots and shortly thereafter the compound under test was applied to the pots in :a drench at the rate of 365 pounds per acre. The pots were placed in a greenhouse and Watered at suitable intervals and the germination and growth of the seeds was compared with similarly planted seeds to which no herbicide was added. In each case, germination was reported on the scale of 0'100%, while growth was reported on a scale of 010, based on the seeds which germinated. Thus, -10 indicates norman germination and normal growth.

The following data were obtained.

The above tests were then repeated using application rates of 10 and 40 pounds per acre with the following results:

Peas Com Radish Rye Cucumber Compound Lbs./ Acre Ge. Gr. Ge. Gr. Ge. Gr. Ge. Gr. Ge. Gr.

10 100 7 100 10 100 10 40 100 3 100 10 100 10 10 100 5 100 100 10 48 100 4 100 10 100 10 $8 DEPLETED 40 10 100 8 100 10 100 10 40 100 4 100 8 100 7 0 100 7 100 10 100 10 15 40 100 4 75 6 75 7 0 10 100 9 100 10 100 10 15 40 100 6 100 8 100 7 0 10 100 8 100 10 100 10 0 40 75 4 100 10 50 3 0 10 100 7 100 10 100 10 0 40 3 100 10 100 10 0 10 100 8 100 10 100 10 0 75 4 100 9 100 8 0 10 100 6 100 10 100 10 0 40 3 100 10 100 10 0 10 100 6 100 10 100 10 0 40 50 3 100 9 100 9 0 8 DEPLETED 10 100 3 100 10 100 3 0 40 100 2 100 9 100 7 0 10 100 4 100 10 100 10 15 40 100 2 100 10 100 10 0 10 100 4 100 10 100 9 0 40 100 2 100 8 25 2 0 10 100 7 100 10 100 10 15 0+ 100 10 40 100 7 100 10 100 7 0 25 3 10 100 9 100 10 100 10 25 0+ 100 10 40 100 8 100 6 100 8 100 6 10 100 10 100 10 100 10 100 3 100 8 40 '100 10 100 4 100 10 50 3 100 8 10 100 4 100 10 100 9 0 75 7 40 50 2 100 7 100 9 0 1 15 0+ 10 100 4 100 10 100 9 0 75 7 40 50 2 100 10 100 9 0 50 3 10 100 4 100 8 100 10 0 100 9 40 25 2 100 6 100 10 0 15 1 10 100 4 100 10 100 10 0 50 5 40 50 2 100 10 100 10 0 15 0+ 10 75 3 100 10 100 9 0 25 7 40 25 1 100 7 100 9 0 15 1 10 100 3 100 10 100 10 0 75 7 40 100 2 100 10 100 10 0 75 7 10 100 3 100 9 100 10 0 50 4 40 75 2 75 5 100 10 o 25 2 10 100 8 100 10 100 10 15 100 10 40 100 7 100 8 100 10 0 25 5 10 100 8 100 10 100 10 75 100 10 40 100 7 100 6 100 10 5 75 8 10 100 6 100 10 100 10 15 100 10 40 25 2 100 8 25 8 0 15 0+ 10 100 10 100 10 100 10 25 100 10 40 100 10 100 10 100 10 10 100 10 10 100 10 100 10 100 10 100 100 8 40 100 7 100 7 100 9 100 10 10 100 7 100 9 100 9 100 100 10 40 100 5 100 8 100 8 100 100 8 10 100 8 100 10 100 9 100 100 10 40 100 5 100 8 100 8 100 8 10 100 8 100 10 100 9 100 2 100 10 40 100 6 100 10 100 8 100 1 100 7 100 8 100 10 100 10 100 1 100 10 40 100 4 100 10 100 8 100 1 100 6 10 100 8 100 10 100 10 100 1 100 10 40 100 5 100 10 100 9 100 0+ 100 10 10 100 7 100 10 100 9 100 1 100 9 40 100 4 100 10 100 7 100 1 100 0 10 100 6 100 10 100 8 100 0+ 70 3 40 100 4 100 9 100 8 25 0+ 15 1 10 100 5 100 10 100 9 0 100 10 40 100 2 100 10 100 8 0 100 3 10 100 8 100 10 100 10 100 0+ 100 7 40 100 5 100 10 100 7 20 0+ 100 4 10 100 6 100 10 100 9 100 0+ 100 10 40 100 2 100 10 100 6 0 50 3 10 100 6 100 10 100 9 20 0+ 100 8 40 100 3 100 10 100 6 10 0+ 100 3 10 100 5 100 10 100 10 10 0+ 100 5 40 100 3 100 10 100 7 0 100 3 1 Percent germination. 2 Growth.

The compounds of the present 1nvent1on may be used We claun: 1n pre-emergence =or post-emergence herb1c1des and may 1. The method of cornbatlng weeds comprising applybe applled 1n a varlety of Ways at var1ous concentratlons. mg a phytotox1c amount to the 8011 of a compound: They may be combmed wlth sultable earners and apphed 0 R2 as dusts, sprays or drenches. The amount apphed w1ll 7 Al depend on the nature of the seeds or plants to be con- S N trolled and the rate of apphcanon may vary from 1 to Rs 500 pounds per acre. One partlcularly advantageous wherem R 1s selected from lower chloroalkyl and bromoway of applymg the compounds 1s as a narrow band alkyl radlcals, R 1s a member selected from the group along arow crop, straddling the row. (I consisting of a lower alkyl radical, a lower chloroalkyl radical, a lower alkenyl radical, a lower chloroalkenyl radical and an alkynyl radical, and R is a member of the group consisting of a lower alkyl radical, a lower cycloalkyl radical, a lower chloroalkyl radical and a lower alkenyl radical.

2. The method of claim 1 wherein the compound is applied at the rate of 1 to 500 pounds per acre.

3. The method of. claim 1 wherein the compound is 2-chloroethyl N,N-di-n-propylthiolcarbamate.

4. The method of claim 1 wherein the compound is 2-bromoethyl N,N-di-n-propylthiolcarbamate.

5. The method of claim 1 wherein the compound is 2-chloroethyl N-ethyl-N-cyclohexylthiolcarbamate.

6. The method of claim 1 wherein the compound is N-allyl-N-isopropylthiolcaroamate.

7. The method of claim 1 wherein the compound is 2-bromoethyl N-methallyl-N-ethylthiolcarbamate.

8. A herbicidal composition comprising a major proportion of a herbicidal adjuvant as carrier and a minor but phytotoxic concentration of a phytotoxic compound of the structure l /N-s-A RI where R and R represent lower alkyl and A represents halogen substituted lower alkyl.

9. The method of destroying vegetation which comprises applying to germinating seedlings a phytotoxic amount of a phytotoxic composition containing as the essential active ingredient a compound of the structure where R and R represent lower alkyl and A represents halogen-substituted lower alkyl.

References (Iited by the Examiner UNITED STATES PATENTS 2,060,733 11/1936 Hunt et al.

2,160,880 6/1939 Loane et a1.

2,562,011 7/1951 Baumgartner 712.7 2,642,451 6/1953 Weijlard et a1 260455 2,687,348 8/1954 Kosmin 712.7 2,901,498 8/1959 Tilles et a1. 712.7 XR 2,901,500 8/1959 Tilles et al. 260455 2,913,327 11/1959 Tilles et al. 71-2.7 2,916,369 12/1959 Tilles et a1. 712.7 2,916,370 12/1959 Tilles et a1. 712.7 2,992,091 7/1961 Harman et al 712.6 2,984,559 5/1961 DAmico 712.7 XR

OTHER REFERENCES Davies et al.: In Chemical Journal, vol. 40, 1946, pages 331334.

Gentner et al.: An Evaluation of Several Chemicals for Their Herbicidal Properties, January 1958, pages 5, 6, and 10, US. Agric. Research Service, Crops Research Div.

Tilles: J.A.C.S., vol. 81, Feb. 5, 1959, pages 714727.

LEWIS GOTTS, Primary Examiner.

M. A. BRINDISI, E. L. ROBERTS, Examiners.

J. P. BRUST, E. J. MEROS, J. O. THOMAS,

Assistant Examiners. 

1. THE METHOD OF COMBATING WEEDS COMPRISING APPLYING A PHYTOTOXIC AMOUNT TO THE SOIL OF A COMPOUND: 